Manufacture of sulphonated oils, fats, fatty acids, and waxes



' Patented N W. 5, 1929 orrc WILLY SECK, or aucsnune, GERMANY, ASSIGNOR '1'0 ERIBA AKrIENGEsELLscnAFr,

or zuarcn, SWITZERLAND MANUFACTURE OF SULPHONATED OILS, FATS,- FATTY ACIDS, AND WAXES No Drawing. Application filed. February 3, 1928, Serial No. 251,737, and in Germany July 28, 1927.

Sulphonated oils-i. e., the commercial products designated by the general term Turkey red oil and preparations similar to Turkey red oil'are employed for widely differing purposes of the industries working with these products (textile industry, leather industry etc.). I

It has now been found, that very many naturally occurring mineral, animal and vegetable fats, oils,'fatty acids and waxes can be converted into sulpho-compounds by the process hereinafter described. Castor oil, linseed oil, rape oil, palm oil and poppy-seed oil, serve as-examples. Further all oils which have undergone treatment, for example, the

blown and boiled oils shown in the manufacture of lineseed-oil'and varnish, as well'as hydrogenated fats and oils can also be subjected to this process. In all these cases the corresponding fatty acids themselves can also be subjected to the sulphonation process.

The sulphonation' process is further not limited to natural oils and fats containing mono-basic fatty acids and to the mono-basic fatty acids themselves but can also be extended to polybasic acids, such as mucic,

adipic, subericorthe like acids, and to oils and fats containing these acids, whether such oils, fats and fatty acids occur in nature as such or are synthetically prepared.

The process is also adapted to numerous substances existing in the large domain of the waxes, for example, japan wax, beeswax, carnauba wax, as well as Montan wax, ceresine and the like. In this case also not only the naturally obtained, but also the synthetically prepared products, can be employed.

The' expression sulphonation is to be under-' stood to include, "besides the action of 5111- phuric acid, treatment of the oils, fats and the like with organic sulpho-acids withor without the addition of sulphuric acid.

. The organic sulpho-acids employed for this purpose may be either aliphatic or aromat c; of the latter B-naphthalenesulphomc acid and its homologues, as Well as the derivatives of these homologues obtained by the addition of alkyl and aryl side chains, are especially suitable. v 4 The sulphonation can further be effected tionwith substances capable of evolving sulphurous acid. In this case it is usually necessary also to subject the oils etc. to oxidation. This oxidation can be effected after the completion of the sulphurous acid action gr at the same time asthe latter. In both cases the oils etc. may be bleached simultaneously with the sulphonation, either by the reducing ac-v tion of the sulphurous acid or by adding a suitable quantity of the oxidizing agent, so that the adition of a special bleaching agent can, under certain circumstances, be dispensed with. It is also possible by this sulphonation process to convert into sulpho-compounds such oils, fats, fatty acids, waxes etc. as, for example, mineral oils of the aliphatic group, which ofi'er considerable difficulties to a conversion of this kind.

The applicability of sulphonated oils of this kind to the widely differing purposes of the industries working with such preparations has hitherto been to a certain extent limited by the colour perculiar to these products. Thus, for example, when using Turkey red oils, finishing oils and like means inthe finishing of white goods, one had always to reckon with an often not inconsiderable spoiling of the whitness of the goods. Similar phenomena were observed in the working up of leather. I Y

It has hitherto not been technically possible to subject Turkey red oils and preparations similar to Turkey red oil to a bleaching process. Furthermore it could not have been foretold whether a preparation of such colourless products could be effected at all, since by sulphonating it might have been just as pos-- sible to give the body obtained a characteristic colour which, as a typical optical property, is inseparably bound with the other known properties of Turkey red oil (i. e. stability in the presence of salts, lime and acid, softeningproperties etc.) L

It has nowbeen unexpectedly discovered ,phonation or after neutralization bleaching that colourless Turkey red oils and preparations similar to Turkey red oil can be Very readily obtained without detriment to the typical Turkey red oil properties of these products. According to the present process, the manufacture of the oil is carried out in the presence of oxidizing or'reducing bleaching agents. When oxidizing bleaching agents are used, these also influence the sulphonation process. On this account such quantities of the oxidizing substances are employed that,

as well as influencing the sulphonation they also effect the bleaching action. The etl'ect is assisted by, on the one hand, sulphonating.

an already bleached oil and, on the other hand, by an after-bleaching of the finished product. The after-bleaching can be effected either directly after the completion of the reaction, whilst the reaction mixture is still acid, or after the subsequent neutralization of the oil.

For the last mentioned preliminary and after-bleaching there may be used, besides the oxidizing or reducing substances, bleaching agents whose bleaching action depends preferably on absorption or adsorption phenomena, unconnected with purely chemical action (fullers earth, etc.)

As oxidizing bleaching agents hydrogen peroxide, as well as all the peroxides and all such substances as are capable of giving off active oxygen in acid solution, especially percompounds such as per-sulpho acids, alkali persulphates, alkali percarbonates. alkali perborates, peroxides of organic acids (such as acetyl peroxide and benzoyl peroxide) compounds of hydrogen peroxide with organic bodies such as benzoic acid and urea, can be used.

For the bleaching process before sulagentse. g. hypochloritesthat are unstable in the presence of acids may also be used.

The following reducing bleaching agents,

Example 1 i 100 kgms. of the palest castor oil, previous- 1y bleached if desired, are sulphonated with 18 kgms. of concentrated sulphuric acid (96 98%) for about four hours. During the sulphonation 16 kgms. of hydrogen peroxide (30%) are added in portions of 4 kgms. at a time. The reaction temperature should. be

about 4050 C. Deviations from this temperature have no great effect. After sulphonation the oil is further treated in the known manner.

li'wample 2 The acid oil is prepared as above except that only 12 kgms. of hydrogen peroxide are used instead of 16 kgms. The pale yellow product obtained after the neutralization is subjected to an after-bleaching by being treated for half an hour at about 60 (lwith 2% l-Igms. of alkali hydrosulphite, with con: tinual stirring. Instead of hydrosulphite one of the oxidizing agents mentioned,-for example, a suitable quantity of sodium, potassium, or calcium hypochlorite-can be employed in the after-bleaching operation.

Example 3 This is the same as Example 1 except that a suitable quantity of sodium, potassium or ammonium persulphate or percarbonate or perborate is employed instead of hydrogen peroxide; otherwise the process is the same as Example 1. When using percarbonate or perborate the quantity of sulphuric acid must be suitably increased on account of its decomposition with these salts.

E mample 4 100 kgms. of the palest castor oil, previously bleached if desired, are sulphonated with 18 kgms. of concentrated sulphuric acid (9698%) for about four hours. During the sulphonation 9 kgms. of 30% hydrogen peroxide are added in portions and, after sulphonation has been effected, a quantity of sodium, potassium, or ammonium persulphate or percarbonate, or of a mixture of, these bodies, corresponding to the remaining 7 kgms. of hydrogen peroxide, is added. The reverse process may also be employed-i. e., the persulphate, pcrcarbonate or perborate may be added during the sulphonation in a quantity corresponding to active oxygen in 9 kgms. of hydrogen peroxide, and 7 kgms. of hydrogen peroxide added after the sulphonation,

Example 5 100 kgms. of oil are treated with 12 kgms. of 30% hydrogen peroxide or with .a corresponding quantity of sodium, potassium or amonium persulphate, percarbonate, or perborate, or mixtures of these bodies, and thereupon, after the sulphonation, 2 kgms. of alkali hydrosulphite or of a compound of formaldehyde with alkali hydrosulphite or alkali sulphoxylate are added to the acid or partially neutralized oil. In this case also as in Example 3 the quantity of sulphuric acid must be suitably increased when per-carbonates or perborates are used.

In all cases, after the sulphonation is comarsaoso plete, the excess of acid is preferably neutralized. This can be efiected by simply washing the oils with water or by adding neutralizing agents such as soda to the fresh sulphonation mixture and washing out the resulting salts or by washing the neutralized oils with suit- 'able organic solvents such as alcohol, ether or the like.- For certain special purposes, however, the oils can also be used with a definite content of free acidi. e., without being neutralized. I

In place of the castor oil mentioned in the examples any of the other oils, fats, fatty acids, and Waxes hereinbefore mentioned can be employed. Other sulphonation methods can also be employed.

Example 6' 109 kgms. of preliminarily bleached palm oil are sulphonated with 18 kgms. of concentrated sulphuric acid (96-98%) for about four hours. During the sulphonation l6 kgms. hydrogen peroxide are added in four portions of 4 kgms. at a time. The reaction temperature is to be kept at about 40 to C. After sulphonation the oil is further worked up in known manner.

Example 7 I The preparation of the acid oil "is carried out as above, but instead of sulphuric acid the same quantity of sulphanilic acid is used together with a suitable catalyst. The further treatment is the same as in the above described example.

Example 8 100 kgms. of a pale japan wax are melted at moderate temperature and are sulphonated with 16 kgms. of sulphanilic acid together with a suitable catalyst, the above described quantity of hydrogen peroxide being added. The further treatment follows in the usual manner, after the neutralization, however, the product is treated by the addition of suitable reagents to render the sulphonated wax liquid at the ordinary temperature.

The production of colourless Turkey .red oil preparations which, on the one hand possess the typical properties of hitherto nown products, and on the other hand, in

' contradistinction to these products, exhibit no partial absorption of light and are thus colourless provides a not unimportant technical advance and renders it possible to use such products to a much more unlimited extent that has beenhitherto possible.

The process further offers the particular advantage that, owing to the presence of bleaching agents in the sulphonation process, a larger number of sulpho groups is taken up by the fats, oils, etc., treated. The oils obtained by this process are consequently distinguished by a greater stability towards limeand salt-containing water, as well as towards acid reacting water etc. used in sub sequent treatments. Finally the products obtained in thisway also possess an'outstanding softening property.

My invention is intended to be utilized for sulphonating oils and fats of animal and plant origin. Hence whenever I refer to oil,"it is undei stood that I refer to an 'oil or fat or fatty acid of animal or plant origin. The improved process produces a new product, namely, a sulphonated and oxidized oil which is stable towards lime/ and magnesia.

The claim for the product is not to be re stricted to the specific process above mentioned.

lVhat I claim is zl. A process for preparing from an oil, fat, fatty acid, or wax, a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent.-

2. A "process for preparing from an oil, fat, fatty acid, or wax, a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent assisting said sulphonation and employed in excess of the quantity required for assisting said sulphonation.

3. A process for preparing'from an oil,

fat, fatty acid, or wax a substantially decol- 6. A process for preparing from an oil,-

fat, fatty acid, or waxa substantially decolorized sulphonated product, consisting of subjecting said substance to a preliminary bleaching operation, thento sulphonation in the presence of a bleaching agent, and then to an after-bleaching operation.

7.-A process for preparing. from an oil,

fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to a preliminary bleaching by a physically acting bleaching I 1 agent and then to sulphonation in the presence of a bleaching agent. 8. A process for preparingv from an oil,

fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent and then to an after-bleaching by a physically acting bleaching agent. 1

9. A process for preparing from an oil, fat, fatty acid, or wax asubstantially decoloi'ized sulphonated product, consisting of subjecting said substance to a preliminary bleaching by a physically acting bleaching agent, then to sulphonation in the presence of a bleaching agent, and then to an afterblcacliing by a physically acting bleaching agent.

10. A process for preparing from an oil, fat, fattyacid, or wax a substantially decolorized sulphonated product, consisting of subjectin said substance to sulphonation in the presence of a bleaching agent, ncutralizing the said sulphonated substance, and then subjecting said ncutralizedsubstance to an after-bleaching operation.

11. A process for preparing from an oil, fat, fatty acid, or wax a substantially decolorized sulphonated product, consisting of subjecting said substance to sulphonation in the presence of a bleaching agent and to an atter-blcaching operation and then neutralizing said bleached and sulphonated substance.

12. A process for preparing from an oil, fat, fatty acid, or Wax a substantially decolorized sulph'onatcd product, consisting of subjecting -said substance to sulphonation by an organic sulpho-acid in the presence of a bleaching agent.

13. A process for preparing from an oil, fat, fatty acid, or Wax a substantially decolorizeil sulphonated product, consisting of subjecting said substance to sulphonation by an organic sulp'ho-acid in the presence of sulphuric acid and a bleaching agent.

14. A substantially decolorized bleached sulphonated oil.

I In testimony whereof I hereunto afiix my signature.

WILLY SEGK. 

